Quinonyl sulphonamides in color compositions



an improved color yieldin printing is not en- ,,tirelyunderstood. Itis wi w or assistants that the presen invention is particularly concerned.

Althoughprinting aids are-desirablein the printing-color pastes, the exact point at which ously contain Patented Feb. 12,- 1946 oumomznsunrnommnnsiuconon .comrosmons Roy Herman and Chester Albert Amick,

Bound Brook. N. 1..

assianm's to American Cyanamid Company, New York, N. Y., a corporation of Maine No Drawing. Application July 1, 1943,

Serial No. 49am a 9 Claims. (01. 8-70) This invention relates to a new type f, ye

ins and printing assistant,-dye compositions con-.

taining these assistants and products printefi therefrom.

Use of printing-color pastes containing dyes, 5 particularly in printing operations using vat dyes...

is sufllciently well known so that the procedure 7 has become almost standardized. The actual color source maybe either a dye paste or a dye powder. ,In addition to the real color, a dye ,10

paste usually contains agents to prevent dryingout, settling and/or freezing. Dye powders, not

being subject to these difilculties, do not require. these agents but they usually contain agents or l are so processed as to promote dispersibility. 15

In either case, the dye paste or dye powder must be admixed with suitable thickener, usually a gum dispersion, to forma printing-color paste which is suitable for application. 'In the caseof vat dyes, it is also necessary to add a reducing 20 agent andusually an alkali. Because the colorv yield from printing-color pastes often decreases I rapidly ;as the paste ages after being made up,

these printing-color pastes are usuallyprepared by She fabric finishers just before they are to be 26 use i 4 'rhe printingecolor pastes, however compounded,.are then applied to textile, paperor oth er fabric materials for decorative or protective purposes. ,The printed pieces are dried, aged in a; steam ager, treated with an oxidizing agent. rinsed I and finally dried. Usually inprocessing textiles,

the printed fabric also is soaped at or near the boil withabout .a 0.1% soap solution and again rinsed before the final drying operation.

, In making up and applying printing-color pastes it has been found that a material suitable for use as a. printing assistant is of'advam tage in obtaining maximumcolor yield. The ex act way in which these materials act to produce ese printingaids i they are added may vary. Dye pastes may contain printing aids as one or their components and; printing-color pastes mad therefrom will obvithe printing a sistant, Wheres arylslflphaminoanthi'aquinones. Unfortunately, "the use of these compounds has several disadvane rinting assistant is not resent inthe 'dye paste,

it may be added, at the time of making-up the1 printing-oolor paste. 1 Y

It is preferable however; the printingas the past include color pastes" s Their addition at the proper point in the manufacture of the paste is not only easier, but in addition they are thus generally more uniformly dispersed throughout a. printing-color paste made therefrom. As a result, the printing assistants usually operate more eifectivelyyhen theprinting-color paste is finally applied to the fab- -ric.-

. It is only relatively recentlythat dye powders suitable for use in making up printing-color pastes have beenzavailable. Most of the printing aids previously used in dye pastes, being either liquid in form or extremely hydroscopic, can not be used with dye powders. the latter being necessarily limited tothe use of dry solids. Never-' theless, it is desirablethat printing assistants be incorporated in the powders at the time of manufacture for the same reasons which apply in the j caseof dyepastes.

Dye pastes containing various .liquid printing assistants have been made. Among the liquid materials used are the alkylol amines, for example, triethanol amine; and/or polyhydrlc alcohols such as glycerine. glycol, diethylene and the like.- Various derivatives therefrom also have been tried. If a printing aid is to be incorporated ina dye powder, a solid printing aid is necessary. Examples of such solids which have'been used in the hydrochlorides of alkylol amines, anthraquinone, silver salt (sodium an-* thraquinone beta-sulphonate) and certain metal salts such as those of cobalt and iron.

Unfortunately, most of these printing aids pre viously used are not as satisfactory as may be to desired. Many of them will not ill all cases produce the intensification of "oolorfor which they were intended. Others, such as the polyhydric alcohols, cause deterioration of the printin ter the pr ting-color paste has been allowed to. stand for only a relatively short time. Many.

ofthem are satisfactory with some colors but have an adverse effect on others, even to the 6x tent of visibly altering the shade. None of them are suitable without modification for use both inpaste and powder compositions.-

qne oithe types; ofcompounds which in the. past has been proposedfor this purpose is theffrom apractical' point of view. It. is'extremely dimcult tov make a suitable formulation with these products. Unless they are in a very sistant beiincorporated in thexactual dye paste. finely. divided condition, prints from pastesconc that marked variations .in the 4 strength of prints therefrom are observable even taining these materials are usually found to be printing, assistants which will produce a satisfactory color intensification, may be readily compounded and will not; cause deterioration of the dyeing or printing composition on standing.

Preferably also, the assistants shouldbe useful both with dye pastes and dye powders and in addition should be readily available or cheaply and easily prepared. It is, therefore, the object of the present invention to provide a new type of printing assistant which possesses these. desirable properties.

In general the objects of the present invention are accomplished by using as a printing assistant a .quinonyl sulphonamide or a derivative thereof represented by the general formula in which Q represents the'residue of a quinone In preparing the sulphonamides used'as printing assistants according to the present invention, the quinonyl radical represented by Q in the generic formula is ordinarily limited to the alphaand beta-anthraquinones and beta-naphthoquinone. The corresponding derivatives of 1,4- naphthoquinone do not appear .to be'capable of being isolated, if they form. In the case of betasuch as alphaor beta-anthraquinone and betanaphthoquinone; R1 and Ba represent hydrogen or alkyl, aryl or alkaryl radicals and :2: may be 1 or 2. Typical of the sulphonamides of the present invention are the monoand disulphonanil ides of beta-anthraquinone which may be 'rep-,

resented by the formulae:

-Use of these compounds was found to have several important advantages. They are completely free from the wetting out problems noted for example in the case of the arylsulphaminoanthraquinones, Being either soluble or readily dispersible in the usual components of dye and printing pastes. they are readily compounded therein. In addition to overcoming difficulties in this respect, they were found in most cases to produce appreciably better color yields. Further, being dry, solid materials, they are particularly well suited for use in dye powder formulations.

So far as the present invention is concerned the assistants may be added "to the printing-color pastes at any-point. They may be incorporated into the thickener; into the dye pastes or powders or may be blended directly into the printingcolor paste. However, as pointed out above. it is preferable that they be incorporated in theg'dye paste or powder. during manufacture. Similarly,

u so desired they may be ed in im w t other printing assistants. I

naphthoquinone, a: in the generic formula is ordinarily'one since the disulphonamides of hetanaphthoquinone are impractical to form.

Inusing' the compounds of the present invention as printing assistants it is not necessary that the application be limited to the use of sulphonamides inwhich R1 and R2 both represent. hydrogen. Such compounds,,however, do make excellent printing assistants. Nor is it necessary that R1 and R2 both represent similar groups. In the present case, sub'stituted-derivatives, for example, in which either R1 or R2 is hydrogen and the other is an alkyl radical, as inthe alpha or betaanthraquinone-su1phonethylide; an aryl radical,

lently as printing assistants with substantially any of the vat dyes. Particularly was this true in the case of the thio-indigoes. Perhaps the most noticeable improvement was found on adding the sulphon-sulphanilids and sulphon-toluidides so that these compounds are perhaps preferable although the invention .is not necessarily meant to be so limited.

While the dye and printing paste compositions of the present invention are not limited to the use of any particular dyes or dye forms. they are especially suitable for use with vat-dyes in eitherv paste or powder form. Particularly good results may be obtained using the vat-dye powders of high-autodispersibility set forth in Cross- 'ley et 9.1., United States Reissue Patent 21,402,

reissued March 19, 1940. By combining the color materials of that patent into printing-paste compositions containing the printing assistants of the present invention, the full advantages of both may be gained with a resultant simplicity in use and excellence of shade and vsharpness of color. Printing pastes made in this way have the particular'advantage that the dyes remain in a highly dispersed state because they aretaken up as individual particles. rather than asdispersion of particle aggregates. In the present specification. and claims, where highly-dispersed dyes are referred to, reference to pastes in which the dye is so dispersed is intended.

' The invention will be'more fully set forth in connection with the following examples which are intended to be illustrative only and not by way of limitations; All parts are by weight unless otherwise noted.

In the succeeding examples, test prints were made on two different fabrics. When rayon is referred to, a titanium-dioxide-pigmented, all viscose-rayon flat crepe was used. The cotton fabric referred to is an x 80 bleached unmercerized, cotton print-cloth. Ageing of the prints was carried out inasteam ager which was con- 7 structed in such a manner thatcontrolled temperatures could be used, The temperature rangev normally used was 10(l'-10 5 C. Those aseinss referred to as 'plantor not ageings were carried amples this mixture is'reierred toss ""am'l',

out in the temperature ranceoi about me -11o C. 1n the case of the cotton-prints ageing periods of 3 minutes,.5 minutesor both were used. On

. Esomple 1' v A paste was repared by slurrying 2.000 parts '0! 177 British gum (Stein Hall) in 5,00013108 of water and the mixture washeated with con-' tinuous. stirring until the temperature reached about 185. 1". Heating was continued for-about no dispersed powder was oars-am so or the thickener Oonlr, Each of these were printed on cotton. The printed pieces were 1% hours after which 450 parts or powderedpotassium' carbonate and 450 parts of powdered sodium carbonate were added and the mixture.

stirred until the carbonates dissolved. Heatinfl wasdiscontinued but was continued until the'temperature reached approximately 150 1 at which time 700 parts of sodium sulphoxylate were dissolved therein, 600 parts of glycerine were added andthe paste bulked to about 10,000

parts. Stirring was continued until the paste cooled to room-temperature. In thesucceeding examples this paste is referred to as thickener A.

' Example 2 2,100 parts or British gum, 200 parts 01 tapioca hour and 500 partsoi cornstarch were added to 2,500 parts of water, and heated over a steam bath for approximately 1% hours after the temperature reached 185 F. The source of heat was then removed but stirring was continued until the temperature decreased to 130 F. at which time 2,100 parts of potassium carbonate which I". Subsequently,.1,400 parts of glycerine were addedand after thorough stirring thewhole w s bulked toabout 10,000 parts. The mixture was cooled and stirred continuously until the mass reached' room temperature. In the succeeding examples this mixture is referred to as thickener B.

Example 3 720 parts or 3-2 British gum and mo-parts or- KAO-4 gum (SteinHall) were added to"5,600 parts oi. water and heated over a steam bathjor approximately'1% hours after the temperature reached 185-190 1". The-source. of heat was then removed but stirring was continued until the temperature. decreased to1201". at which time, .1200 parts. r potassium-carbonate which been previously v watergwasadded to the cooked gum. 1,500 parts or sodiumfsulphoxylate tormaldehyde'were disof about-140* Puntil the whole wasthoroughlv mixed. parts or glycerine were add-. ed and after thorough; bulked to 12.00 parts. In the succeeding exthickener-c. I armour-f 10 parts prepared according to United. States Reissue'Patent31.402 and containing approximately 8.! parts or real dye-were dry blended with 0.3 Pitts of anthraqu none-beta-siflnhonanilid. after which 89.! parts of thickener C were addeduandflthor- 01181 it seeond'mpartl oIDark Blue dissolved in 1,000 parts of.

stirring the whole was ota Dark Blue BO dispersedpowder.

A sample of wet presscake of Vat Orange R air dried, aged, oxidised one: the lid?!) for minutes in a 11:96 soap solution at theboil Y The procedure Example was duplicated that Golden Orange (3 (C. 1.4098) cone except taining about 1.9 parts of real dye wassubstituted and brighter than those made from the paste which containednoassistant. V

trample 0 (C; I.-121'7) was dispersed with the sodium salt oi disulfo-dinaphthylmethane, and adjusted-with water to contain 12% real dye. To parts of this mixture was added 0.3 parts of beta-antbra-' quinonyl sulphonanilid and 90 parts of thickener I O. A duplicate sample was also prepared except taining'the printing assistant were deflnitelysu periortothcse from theblank. v I p Example 6 we beta-anthraquinonylthat no anthraquinone-beta-sulphonanilid wa added. Each of these pastes were tested on mama and cotton. The prints from the paste containing the, anthraquinone-beta sulphonanilld"were" Jrmich stronger and brighter gthan those obtained the paste which had been previously dissolved v.in' hot water was added to the cooked gum.. 1,100 parts of sodium r. formaldehyde sulphoxylate were added to the common mixture at a temperature of about 150 tainedno assistant.

ain

phona'nilid'. Again-the prints from the paste'conof Cerelwe and the milling was continued for 18 hours. 10 parts or the above product which coni tained about 2.4 parts or real dye were then mixed and'inixed with parts 01' thickener A to make acontrol paste. ot'these pastes were printed p The prints from the paste containing I with 90 parts or thickener A. A'second parts.

01' the concentrated Orange R powder-1 were also ball milled with 89- parts or Cei'elose ior 21 hours on the" anthraquinone-beta-sulphonanilid gave much.

- stronger and brighter prints than those iron: the Cerelose only.

, ThezprocedureoiExample 1 8 99 j we .101.

cant that a: or bet phonanide v ed. substituting V 'honethylide for the sulw lj v e es-mjthat alpha-anthraquinonrl sulphonanilid used in place or the beta-derivativej.; ub-- 3T1; stantially. identical results were obtained.

4 acacia taining Cerelose only.

Example 11 The 11.4 showing that the print from the paste concept that the alpha-anthraquinonvl-sulphonamide was used in place of the beta-sulphonamide. Prints obtained from the paste containingthealpha-anthraquinonyl sulphonamideWere substantially the same as those from the paste containing the beta-derivative or Exsmple'9.

sample 12 Examples was again repeated except that the anthraquinone-beta-sulphonanilid was replaced by beta anthraquinonyl sulphon' p toluidide.

Alter milling 10 parts oi. this mixture were mixed with 90parts o1 thickener form a printing paste. 10 parts of the sample were also mixed with 90 parts'oifStliick'ener 3 also. Each of thesepa'stes were prlnted on rayon. Prints trample 13 The procedure oi Example 12 was followed exactly except that the beta-anthraquinonyl-sulphon-p-toluidide was replaced by alpha-anthraquinonyl derivative. Again itwas found that interchanging'the alphaand beta-anthraquinones gave substantially thesame color yields on a basis of true color content in the printing pastes.

Emmi 1 Again the procedure oi Example 12 was lol- 1 lowed, using beta-anthraquinonyl sulphonamidebenzene sulphcnic acid as the printing assistant. Again, marked improvement in the color. yield from paste containing the assistant was obtained.

Example 15 -'900partsoiVatPink1"Fpresscakewerede-- ilocculated with the sodium salt oi disulpho-' mmlud dinaphthylmethane then passed through a colloid mill to give a smooth; uniiorm su'spcnsion. This product was'called "Vat Pink 1"! deflocculated press cake." After determining the a was assistant; arr-improvement oi approximately 47% over prints'i'rom the paste containing-water only. p Example 16 v The procedure of Example 16 was repeated exactly except that the beta-anthraquinonyl sul-' phonamlde was replaced by beta-anthraquinonyl sulphon -p-toluidide. The "efliciency factor" was "lining the anthraquincne b'eta-sulphon-ptoluidide was approximately'wfi stronger than the print irom the paste containing water only. Erample i7 15 The printing assistants oi'hxamples 8 and 10 were again tested using thickener 3. Again the I prints obtained from the pastes containing the printing ts were stronger and brighter than those obtained from the pastes containing Cerelose only indicating that the'improved efl'ect produced by the anthraquinonyl-sulphon-derivatives is not due to a particular thickener used in making up the printing paste.

We claim: I

35 l. A color composition prising a vat dye and a quinonyl sulphonamidehavina the general formula 1 so I o f Q in which Q represents aquinonyl radical selected from the group consisting of the beta-naphtho- 35 quinonyl and the anthraquinonyl radicals, R1

represents a radical selected from the group consisting of hydrogen and the alkyl, aryl and alkaryl radicals and z is a small whole number-selected from he group consisting of Land 2.

2. A dye powder composition comprising a vat" dye and a powdered quinonyl sulphonamide havinathegcnerali'crmula in which Q represents a quinonyl radical selected from the group consisting of the beta-naphthowater was added to reduce the dye content in A M 24 hours. This 16% ,Pink 1'! water paste was called ;theblank'. 'A second quantity or Vatdd.

. batch approximately to partial pure .dxewasgroundina'ballmiilwithspartscibetidye content oi this material. a weighed Quantity 5 mum I: I was entered in a ball mill.- To this mass enoughpmmde deny-av seem A. =1

' in which dreamt",

approximately 15% and the mix 'was'ground ior- Pink I'l'deiiocculated press cake item the same 1 1 i quinonyl radical selected an hraquinonyl'sulphonamide and, enough from the group consistingotthc-ibeta-inaphthoto reduce content-to 16%. 6', guinonylandth'eanthraquinonyl radicals. m represents a radicals'electcd iromthe group conthen -'anaiysedi3ier;extracted aolids;.a'nd "listing or hyth'ogen' and the'alhrlgaryla'nd alka'ryl eien 'cy'" determined. mamas-brine andr is a "man whole number selected was at e-5.2m samples from the 1.,

- cotton 1m 7o "lilo; orcclervahieoontaining-ths'printing j the-.xprintsde'tsi'mind, callrandltha sistant over the blank] were;

iactoriwas 1.47.

high autodispersibility and the quinonyl y dnmthickcnerandaquinonyl'sulphonamide havingthegeneraltormula in which Q. represents a qulnonyl radical selected fromthe group consisting or the betanaphthoquinonyl and anthraquinonyl R1 represents a radical selected from the group consisting of hydrogen and the 1,1171 and alkaryl radicals and: is a small whole number selected from the group. consisting of 1 and 2.

..7. it printing paste composition comprising a highly-dispersed vat ,dye, a thickener and' a quinenyl sulphonamide haying the general iormule " in which name. quinonylr a diealselected from the group consisting or the beta-naphthoquinonyl and anthraquinonyl radicals, R1 represents 'a radical selected from-the group consisting or hydrogen and the aikyl, axyl and alka'ryl radicals and z is a small whole number selected from the group c'onsistingot land 2, obtainable by compounding a colloidiaed vat dye powder or phonamide with the thickener s. m otprinting wlth m colors which comprises printing a fabric with a printing paste composition comprising a vet dye. a thickener and a quinonyl sulphonamide havin the general formula w m which Q represents a quinonyl radical smeared from the group consisting of the beta-naphthoric printed with a composition comprising avvat dye and a quinonyl general formula I in which Q represents a quinonyl radical selected sulphonamide having the from the group consisting oi the beta-naphthaquinopyl and theanthraquinonylradicala' R1 represents a radical selected from the group consisting of hydrogen and the alkyl, aryl and alkaryl radicals and a: is a small whole number selected fromthe group consisting of 1 and 2.

'- ROY C ALBERT AMICK. 

